tert-Butyl N-(4-hy­droxy­benz­yl)-N-[4-(prop-2-yn­yloxy)benz­yl]carbamate

Ao, L.; Tu, J.-H.; Huang, X.; Ding, B.-Y.

doi:10.1107/S160053681103683X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2642

https://doi.org/10.1107/S160053681103683X

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tert-Butyl N-(4-hydroxybenzyl)-N-[4-(prop-2-ynyloxy)benzyl]carbamate

Lei Ao,^a ^* Jie-Hong Tu,^a Xuan Huang ^a and Bao-Yue Ding ^a

^aCollege of Medicine, Jiaxing University, Jiaxing 314001, People's Republic of China
^*Correspondence e-mail: aolei.1997@163.com

(Received 9 August 2011; accepted 11 September 2011; online 14 September 2011)

In the crystal structure of the title compound, C₂₂H₂₅NO₄, intermolecular O—H⋯O hydrogen bonds involving the hydroxy group of the 4-(amimomethyl)phenol fragment and the C=O group connect the molecules into infinite chains along the c axis. Two C atoms of the propyne group are disordered over two sites with occupancy factors of 0.53 (2) and 0.47 (2).

Related literature

For applications of the title compound, see: Späth & König (2010 ); Juríček et al. (2011 ). For the synthesis of the title compound, see: Kim et al. (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₂H₂₅NO₄
M_r = 367.43
Monoclinic, P 2₁ /c
a = 18.6904 (8) Å
b = 6.2611 (4) Å
c = 17.3567 (7) Å
β = 96.791 (1)°
V = 2016.87 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.41 × 0.37 × 0.29 mm

Data collection

Rigaku R-AXIS RAPID/ZJUG diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.957, T_max = 0.976
15741 measured reflections
3750 independent reflections
2099 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.149
S = 1.00
3750 reflections
268 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱ	0.82	1.94	2.745 (2)	167
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681103683X/kj2185sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681103683X/kj2185Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681103683X/kj2185Isup3.cml

checkCIF report

Comment top

The amino group is one of the most important functional groups in molecules of biological relevance, of which histamine and dopamine are two representative examples. In the synthesis of amino-contaning compounds, the boc group is commonly used to protect the amino group when performing parallel chemical transformations (Späth et al. , 2010). The acetylene group, due to the presence of the carbon-carbon triple bond, is an ideal functional group for further postmodification by numerous synthetic transformations (Juríček et al. , 2011). In our exploration of structure-activity relationships of amino-contaning compounds, we recently obtained a crystal of an intermediate, which contains both a boc-protecting amino group and an acetylene group. We report its crystal structure here.

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle of the rings C1—C6 and C9—C14 is 11.7 (3)°. The bond lengths and angles are within normal ranges (Allen et al., 1987). The C18—N1 distance is 1.348 (3) Å, which is in the range of a typical double C=N bond. Atom O4 has a partial anionic character, as is shown by the lengthening of the C=O bond [1.226 (3) Å] compared to what is normally found for carbonyl groups. This atom acts as a hydrogen-bond acceptor for an intermolecular O—H···O hydrogen bond (Table 1). The hydrogen bonds are forming one-dimensional infinite chains along the c axis (Fig. 2).

Related literature top

For applications of the title compound, see: Späth & König (2010); Juríček et al. (2011). For the synthesis of the title compound, see: Kim et al. (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized according to the method proposed by Kim et al. (2004). 4-(Amimomethyl)phenol (0.01 mol,1.23 g) and 4-(prop-2-gnyloxy)benzoldehyde were heated in anhydrous methanol for 2 h, then NaBH₄ (0.1 mol,0.38 g) was added to the solution. The resulting solution was stirred for 30 minutes, then Boc₂O (0.01 mol,2.18 g) was dropped into the solution. Colourless block-shaped single crystals suitable for X-ray structure determination were obtained by slow evaporation of the solution in a mixture of PE:EA(1:1,v:v). Yield: 51.7%.

Structure description top

For applications of the title compound, see: Späth & König (2010); Juríček et al. (2011). For the synthesis of the title compound, see: Kim et al. (2004). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of title compound. Displacement ellipsoids are drawn at the 40% probability level. Only the major disorder component is shown.
	Fig. 2. Crystal packing of the title compound, viewed down the b axis, showing the O—H···O the hydrogen bonds as green dashed lines. H atoms not involved in hydrogen bonding have been omitted. Both disorder compounds of the propyne group are shown.

tert-Butyl N-(4-hydroxybenzyl)-N-[4-(prop-2-ynyloxy)benzyl]carbamate top

Crystal data top

C₂₂H₂₅NO₄	F(000) = 784
M_r = 367.43	D_x = 1.210 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9726 reflections
a = 18.6904 (8) Å	θ = 3.0–27.4°
b = 6.2611 (4) Å	µ = 0.08 mm⁻¹
c = 17.3567 (7) Å	T = 296 K
β = 96.791 (1)°	Chunk, colorless
V = 2016.87 (18) Å³	0.41 × 0.37 × 0.29 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID/ZJUG diffractometer	3750 independent reflections
Radiation source: rolling anode	2099 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.5°, θ_min = 3.0°
ω scans	h = −22→22
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −7→7
T_min = 0.957, T_max = 0.976	l = −21→19
15741 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0635P)² + 0.6687P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
3750 reflections	Δρ_max = 0.26 e Å⁻³
268 parameters	Δρ_min = −0.19 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0155 (18)

Crystal data top

C₂₂H₂₅NO₄	V = 2016.87 (18) Å³
M_r = 367.43	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.6904 (8) Å	µ = 0.08 mm⁻¹
b = 6.2611 (4) Å	T = 296 K
c = 17.3567 (7) Å	0.41 × 0.37 × 0.29 mm
β = 96.791 (1)°

Data collection top

Rigaku R-AXIS RAPID/ZJUG diffractometer	3750 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2099 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.976	R_int = 0.038
15741 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	4 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
3750 reflections	Δρ_min = −0.19 e Å⁻³
268 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.17241 (12)	0.2936 (3)	0.76205 (9)	0.0818 (6)
H1	0.1833	0.3985	0.7892	0.123*
O2	0.43006 (9)	0.6806 (3)	0.13104 (10)	0.0726 (5)
O3	0.13748 (8)	0.5836 (3)	0.40395 (8)	0.0592 (5)
O4	0.19445 (10)	0.8841 (3)	0.36950 (9)	0.0695 (5)
N1	0.25604 (11)	0.6051 (3)	0.42845 (10)	0.0605 (5)
C1	0.19319 (13)	0.3250 (4)	0.68966 (12)	0.0564 (6)
C2	0.22502 (14)	0.5106 (4)	0.66891 (13)	0.0643 (7)
H2	0.2334	0.6214	0.7046	0.077*
C3	0.24466 (15)	0.5329 (4)	0.59494 (13)	0.0664 (7)
H3	0.2663	0.6593	0.5816	0.080*
C4	0.23302 (11)	0.3722 (4)	0.54024 (12)	0.0513 (6)
C5	0.20066 (14)	0.1883 (4)	0.56236 (13)	0.0648 (7)
H5	0.1919	0.0776	0.5268	0.078*
C6	0.18094 (15)	0.1640 (4)	0.63598 (14)	0.0712 (7)
H6	0.1592	0.0378	0.6493	0.085*
C7	0.25534 (14)	0.3881 (4)	0.45966 (13)	0.0633 (7)
H7A	0.3032	0.3276	0.4604	0.076*
H7B	0.2227	0.3019	0.4248	0.076*
C8	0.32381 (13)	0.7155 (5)	0.42417 (13)	0.0712 (8)
H8A	0.3601	0.6535	0.4622	0.085*
H8B	0.3180	0.8639	0.4382	0.085*
C9	0.35077 (12)	0.7072 (4)	0.34535 (12)	0.0584 (6)
C10	0.39496 (15)	0.8655 (5)	0.32395 (15)	0.0776 (8)
H10	0.4067	0.9780	0.3581	0.093*
C11	0.42283 (15)	0.8647 (5)	0.25335 (15)	0.0762 (8)
H11	0.4527	0.9746	0.2404	0.091*
C12	0.40561 (12)	0.6991 (4)	0.20300 (13)	0.0579 (6)
C13	0.36058 (13)	0.5388 (4)	0.22214 (14)	0.0649 (7)
H13	0.3485	0.4271	0.1877	0.078*
C14	0.33342 (13)	0.5442 (4)	0.29254 (14)	0.0652 (7)
H14	0.3027	0.4359	0.3049	0.078*
C15	0.48249 (14)	0.8306 (4)	0.11323 (15)	0.0756 (8)
H15A	0.5194	0.8459	0.1571	0.091*
H15	0.4601	0.9688	0.1024	0.091*	0.532 (4)
H15B	0.5046	0.7474	0.0752	0.091*	0.468 (4)
C16A	0.5155 (2)	0.7544 (7)	0.0443 (2)	0.0661 (14)	0.532 (4)
C17A	0.5407 (3)	0.6902 (8)	−0.0069 (2)	0.0760 (17)	0.532 (4)
H17A	0.5615	0.6372	−0.0491	0.091*	0.532 (4)
C16B	0.4509 (3)	1.0432 (7)	0.0868 (3)	0.0689 (17)	0.468 (4)
C17B	0.4307 (4)	1.2108 (7)	0.0727 (4)	0.086 (2)	0.468 (4)
H17B	0.4141	1.3484	0.0611	0.103*	0.468 (4)
C18	0.19532 (13)	0.7046 (4)	0.39779 (12)	0.0566 (6)
C19	0.06391 (13)	0.6547 (4)	0.37645 (14)	0.0623 (6)
C20	0.05670 (17)	0.6953 (5)	0.28996 (16)	0.0932 (10)
H20A	0.0806	0.8265	0.2800	0.140*
H20B	0.0066	0.7054	0.2703	0.140*
H20C	0.0783	0.5797	0.2647	0.140*
C21	0.01977 (15)	0.4612 (5)	0.39359 (16)	0.0809 (8)
H21A	0.0320	0.3431	0.3624	0.121*
H21B	−0.0306	0.4932	0.3818	0.121*
H21C	0.0299	0.4245	0.4475	0.121*
C22	0.04566 (18)	0.8454 (5)	0.4239 (2)	0.1049 (11)
H22A	0.0587	0.8160	0.4780	0.157*
H22B	−0.0051	0.8734	0.4144	0.157*
H22C	0.0718	0.9680	0.4093	0.157*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1286 (16)	0.0695 (13)	0.0529 (10)	−0.0072 (12)	0.0346 (10)	0.0001 (9)
O2	0.0827 (12)	0.0748 (13)	0.0651 (11)	−0.0114 (10)	0.0292 (9)	−0.0031 (9)
O3	0.0653 (10)	0.0561 (10)	0.0566 (9)	0.0006 (8)	0.0088 (7)	0.0070 (8)
O4	0.0927 (13)	0.0557 (11)	0.0608 (10)	−0.0063 (9)	0.0113 (9)	0.0095 (8)
N1	0.0651 (12)	0.0708 (14)	0.0463 (10)	0.0014 (11)	0.0101 (9)	0.0085 (10)
C1	0.0717 (15)	0.0532 (15)	0.0454 (12)	0.0012 (12)	0.0109 (11)	0.0046 (11)
C2	0.0915 (18)	0.0562 (16)	0.0455 (13)	−0.0079 (14)	0.0090 (12)	−0.0060 (11)
C3	0.0921 (18)	0.0566 (16)	0.0522 (14)	−0.0155 (13)	0.0155 (13)	−0.0014 (12)
C4	0.0559 (13)	0.0566 (15)	0.0412 (11)	0.0052 (11)	0.0046 (9)	0.0014 (10)
C5	0.0825 (17)	0.0591 (16)	0.0529 (14)	−0.0081 (13)	0.0089 (12)	−0.0107 (12)
C6	0.102 (2)	0.0533 (16)	0.0612 (15)	−0.0136 (14)	0.0206 (14)	−0.0054 (12)
C7	0.0765 (16)	0.0657 (17)	0.0485 (13)	0.0155 (13)	0.0105 (11)	0.0065 (11)
C8	0.0694 (16)	0.093 (2)	0.0519 (13)	−0.0119 (15)	0.0077 (12)	−0.0025 (13)
C9	0.0558 (13)	0.0720 (17)	0.0475 (12)	−0.0059 (12)	0.0061 (10)	0.0016 (12)
C10	0.0908 (19)	0.087 (2)	0.0562 (15)	−0.0329 (17)	0.0127 (14)	−0.0139 (14)
C11	0.0831 (18)	0.084 (2)	0.0631 (16)	−0.0333 (16)	0.0160 (13)	−0.0054 (14)
C12	0.0586 (13)	0.0661 (16)	0.0506 (13)	0.0006 (12)	0.0131 (11)	0.0036 (12)
C13	0.0726 (16)	0.0621 (16)	0.0632 (15)	−0.0091 (13)	0.0215 (12)	−0.0066 (12)
C14	0.0676 (15)	0.0668 (17)	0.0636 (15)	−0.0105 (13)	0.0179 (12)	0.0011 (13)
C15	0.0773 (18)	0.078 (2)	0.0759 (17)	−0.0071 (15)	0.0281 (14)	0.0091 (15)
C16A	0.074 (3)	0.065 (3)	0.059 (3)	−0.008 (3)	0.006 (2)	0.015 (2)
C17A	0.099 (4)	0.082 (4)	0.052 (3)	0.004 (3)	0.032 (3)	0.003 (3)
C16B	0.078 (4)	0.074 (4)	0.058 (3)	−0.014 (3)	0.022 (3)	−0.009 (3)
C17B	0.124 (6)	0.056 (4)	0.083 (4)	−0.005 (4)	0.030 (4)	−0.002 (3)
C18	0.0739 (16)	0.0567 (16)	0.0407 (12)	−0.0044 (13)	0.0126 (11)	−0.0007 (11)
C19	0.0630 (14)	0.0604 (16)	0.0641 (14)	0.0043 (12)	0.0096 (12)	−0.0031 (12)
C20	0.100 (2)	0.100 (2)	0.0728 (17)	−0.0091 (19)	−0.0149 (16)	0.0252 (17)
C21	0.0818 (18)	0.080 (2)	0.0820 (19)	−0.0154 (16)	0.0134 (15)	0.0000 (15)
C22	0.091 (2)	0.078 (2)	0.150 (3)	0.0079 (17)	0.034 (2)	−0.037 (2)

Geometric parameters (Å, º) top

O1—C1	1.372 (3)	C10—H10	0.9300
O1—H1	0.8200	C11—C12	1.369 (3)
O2—C12	1.385 (3)	C11—H11	0.9300
O2—C15	1.417 (3)	C12—C13	1.376 (3)
O3—C18	1.335 (3)	C13—C14	1.378 (3)
O3—C19	1.470 (3)	C13—H13	0.9300
O4—C18	1.226 (3)	C14—H14	0.9300
N1—C18	1.348 (3)	C15—C16A	1.488 (3)
N1—C8	1.452 (3)	C15—C16B	1.506 (3)
N1—C7	1.464 (3)	C15—H15A	0.9700
C1—C2	1.373 (3)	C15—H15	0.9700
C1—C6	1.374 (3)	C15—H15B	0.9700
C2—C3	1.383 (3)	C16A—C17A	1.128 (3)
C2—H2	0.9300	C16A—H15B	0.5978
C3—C4	1.383 (3)	C17A—H17A	0.9300
C3—H3	0.9300	C16B—C17B	1.132 (3)
C4—C5	1.376 (3)	C17B—H17B	0.9300
C4—C7	1.509 (3)	C19—C22	1.512 (4)
C5—C6	1.379 (3)	C19—C20	1.513 (4)
C5—H5	0.9300	C19—C21	1.515 (4)
C6—H6	0.9300	C20—H20A	0.9600
C7—H7A	0.9700	C20—H20B	0.9600
C7—H7B	0.9700	C20—H20C	0.9600
C8—C9	1.514 (3)	C21—H21A	0.9600
C8—H8A	0.9700	C21—H21B	0.9600
C8—H8B	0.9700	C21—H21C	0.9600
C9—C10	1.369 (3)	C22—H22A	0.9600
C9—C14	1.384 (3)	C22—H22B	0.9600
C10—C11	1.387 (3)	C22—H22C	0.9600

C1—O1—H1	109.5	C14—C13—H13	120.1
C12—O2—C15	116.86 (19)	C13—C14—C9	121.6 (2)
C18—O3—C19	122.50 (19)	C13—C14—H14	119.2
C18—N1—C8	117.3 (2)	C9—C14—H14	119.2
C18—N1—C7	122.1 (2)	O2—C15—C16A	109.0 (3)
C8—N1—C7	120.4 (2)	O2—C15—C16B	113.3 (3)
C2—C1—O1	122.7 (2)	C16A—C15—C16B	102.9 (3)
C2—C1—C6	119.1 (2)	O2—C15—H15A	109.9
O1—C1—C6	118.3 (2)	C16A—C15—H15A	109.9
C1—C2—C3	120.0 (2)	C16B—C15—H15A	111.6
C1—C2—H2	120.0	O2—C15—H15	109.9
C3—C2—H2	120.0	C16A—C15—H15	109.9
C4—C3—C2	121.8 (2)	H15A—C15—H15	108.3
C4—C3—H3	119.1	O2—C15—H15B	98.9
C2—C3—H3	119.1	C16B—C15—H15B	116.8
C5—C4—C3	117.1 (2)	H15A—C15—H15B	105.5
C5—C4—C7	119.5 (2)	H15—C15—H15B	123.8
C3—C4—C7	123.4 (2)	C17A—C16A—C15	177.7 (5)
C4—C5—C6	121.7 (2)	C17A—C16A—H15B	154.1
C4—C5—H5	119.2	C16A—C17A—H17A	180.0
C6—C5—H5	119.2	C17B—C16B—C15	173.8 (6)
C1—C6—C5	120.4 (2)	C16B—C17B—H17B	180.0
C1—C6—H6	119.8	O4—C18—O3	125.5 (2)
C5—C6—H6	119.8	O4—C18—N1	123.5 (2)
N1—C7—C4	114.8 (2)	O3—C18—N1	111.0 (2)
N1—C7—H7A	108.6	O3—C19—C22	109.0 (2)
C4—C7—H7A	108.6	O3—C19—C20	110.1 (2)
N1—C7—H7B	108.6	C22—C19—C20	114.1 (3)
C4—C7—H7B	108.6	O3—C19—C21	101.8 (2)
H7A—C7—H7B	107.5	C22—C19—C21	111.2 (2)
N1—C8—C9	114.55 (19)	C20—C19—C21	110.0 (2)
N1—C8—H8A	108.6	C19—C20—H20A	109.5
C9—C8—H8A	108.6	C19—C20—H20B	109.5
N1—C8—H8B	108.6	H20A—C20—H20B	109.5
C9—C8—H8B	108.6	C19—C20—H20C	109.5
H8A—C8—H8B	107.6	H20A—C20—H20C	109.5
C10—C9—C14	117.1 (2)	H20B—C20—H20C	109.5
C10—C9—C8	119.8 (2)	C19—C21—H21A	109.5
C14—C9—C8	123.1 (2)	C19—C21—H21B	109.5
C9—C10—C11	122.6 (2)	H21A—C21—H21B	109.5
C9—C10—H10	118.7	C19—C21—H21C	109.5
C11—C10—H10	118.7	H21A—C21—H21C	109.5
C12—C11—C10	118.8 (2)	H21B—C21—H21C	109.5
C12—C11—H11	120.6	C19—C22—H22A	109.5
C10—C11—H11	120.6	C19—C22—H22B	109.5
C11—C12—C13	120.2 (2)	H22A—C22—H22B	109.5
C11—C12—O2	124.1 (2)	C19—C22—H22C	109.5
C13—C12—O2	115.7 (2)	H22A—C22—H22C	109.5
C12—C13—C14	119.7 (2)	H22B—C22—H22C	109.5
C12—C13—H13	120.1

O1—C1—C2—C3	−179.9 (2)	C10—C11—C12—C13	0.9 (4)
C6—C1—C2—C3	−0.4 (4)	C10—C11—C12—O2	−180.0 (2)
C1—C2—C3—C4	0.1 (4)	C15—O2—C12—C11	7.5 (4)
C2—C3—C4—C5	0.2 (4)	C15—O2—C12—C13	−173.4 (2)
C2—C3—C4—C7	−178.4 (2)	C11—C12—C13—C14	−0.6 (4)
C3—C4—C5—C6	−0.4 (4)	O2—C12—C13—C14	−179.8 (2)
C7—C4—C5—C6	178.3 (2)	C12—C13—C14—C9	−0.5 (4)
C2—C1—C6—C5	0.3 (4)	C10—C9—C14—C13	1.3 (4)
O1—C1—C6—C5	179.8 (2)	C8—C9—C14—C13	−178.2 (2)
C4—C5—C6—C1	0.1 (4)	C12—O2—C15—C16A	165.7 (3)
C18—N1—C7—C4	−79.6 (3)	C12—O2—C15—C16B	−80.4 (3)
C8—N1—C7—C4	105.1 (2)	C19—O3—C18—O4	0.1 (3)
C5—C4—C7—N1	151.9 (2)	C19—O3—C18—N1	178.88 (18)
C3—C4—C7—N1	−29.5 (3)	C8—N1—C18—O4	−2.7 (3)
C18—N1—C8—C9	−77.4 (3)	C7—N1—C18—O4	−178.1 (2)
C7—N1—C8—C9	98.1 (3)	C8—N1—C18—O3	178.44 (18)
N1—C8—C9—C10	154.0 (3)	C7—N1—C18—O3	3.0 (3)
N1—C8—C9—C14	−26.5 (4)	C18—O3—C19—C22	−64.6 (3)
C14—C9—C10—C11	−1.1 (4)	C18—O3—C19—C20	61.2 (3)
C8—C9—C10—C11	178.5 (3)	C18—O3—C19—C21	177.9 (2)
C9—C10—C11—C12	−0.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.82	1.94	2.745 (2)	167

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₅NO₄
M_r	367.43
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	18.6904 (8), 6.2611 (4), 17.3567 (7)
β (°)	96.791 (1)
V (Å³)	2016.87 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.41 × 0.37 × 0.29

Data collection
Diffractometer	Rigaku R-AXIS RAPID/ZJUG
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.957, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	15741, 3750, 2099
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.149, 1.00
No. of reflections	3750
No. of parameters	268
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.19

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.82	1.94	2.745 (2)	167

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The authors thank Mr Jian Ming Gu of the X-ray crystallographic facility of Zhejiang University for assistance with the crystal structure analysis.

References

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